Photosensitive polyimide composition and polyimide precursor composition

ABSTRACT

There is provided a photosensitive composition including a polyimide or polyimide precursor. The polyimide and polyimide precursor of the present invention includes a group of a first acid-cleavable group, a first base-cleavable group or a first thermally-cleavable group, and another group of a hydrophilic group, or a protected hydrophilic group by a second acid-cleavable group, a second base-cleavable group, or a crosslinkable group.

TECHNICAL FIELD

The present invention relates to a novel photosensitive compositionincluding a polyimide or a polyimide precursor.

BACKGROUND

Photosensitive compositions including a polyimide/polyimide precursor(or polyamic acid) have been widely used to form polymer relief patternsserving as insulation or passivation films for very large scaleintegration (VLSI) and multichip modules (MCM) because polyimides haveexcellent properties especially in terms of thermal stability andchemical resistance. Conventionally, the photosensitive compositionsinclude a photosensitive additive, which serves to control thedissolution rate of the composition into an alkaline developer solution.The dissolution rate into the developer solution can be differentiatedbetween the exposed region and the non-exposed region, thereby allowingdevelopment of a pattern. The developed pattern is subjected to anappropriate thermal process to form a relief pattern.

In the case of conventional polyimides used in photosensitivecompositions, the polyimide includes alkaline soluble groups. However,once the photosensitive compositions are formed into a relief pattern,those alkaline soluble groups should be removed because they cannegatively impact the desired physiochemical properties of the polyimiderelief pattern. For example, the presence of such alkaline solublegroups can result in higher water absorbance and higher dielectricconstants than in a similar polymer without such groups. In order toremove the alkaline soluble groups, the developed pattern generally hasto be heated at a high temperature, e.g., at 320° C. or more.

Thus, one objective of the present invention is to provide aphotosensitive composition including a polyimide, which can be formedinto a relief pattern at a lower temperature. Another objective is toprovide a photosensitive composition including a polyimide, whosealkaline soluble groups can be removed after developing a polyimidepattern at a lower temperature. A further objective of the presentinvention is to provide a photosensitive composition including apolyimide precursor, whose alkaline soluble groups can be removed afterdeveloping a polyimide pattern at a lower temperature.

SUMMARY OF THE INVENTION

According to the first aspect of the present invention, there isprovided a photosensitive composition including: a polyimide comprisinga repeating unit as represented by Formula 1:

In Formula 1, R1 represents an aliphatic, alicyclic, aromatic orheterocyclic group; R2 represents an aliphatic, alicyclic, aromatic orheterocyclic group; R3 represents a bifunctional or more organic groupselected from the group containing a first acid-cleavable group, firstbase-cleavable group or first thermally-cleavable group; R4 represents amonofunctional hydrophilic group or a monofunctional hydrophilic groupprotected by second acid-cleavable group, second base-cleavable group,or crosslinkable cleavable group; and, h represents an integer of 1 ormore. In particular, h represents 1 or more and 8 or less in oneembodiment; and h represents 1 or more and 4 or less in anotherembodiment; and h represents 1 or 2 in yet another embodiment.Generally, h corresponds to the number minus 1 of the functionality ofR3. The photosensitive composition further includes a photosensitiveadditive.

Since a pre-formed polyimide is used, conversion of polyamic acids intoa polyimide is not involved, and thus the relief pattern can be formedat a lower temperature. R4 can change the alkali solubility of thepolyimide when the photosensitive composition is irradiated to actiniclight. The photosensitive composition of the present invention can beprepared either in a positive type or a negative type. R3 can be cleavedafter developing a pattern, so that the groups of R3 and R4, including ahydrophilic group, can be removed, resulting in improved stability andreliability of the relief pattern.

According to the second aspect of the present invention, there isprovided a photosensitive composition including: a polyimide precursorcomprising a repeating unit as represented by Formula 2:

In Formula 2, R1 represents an aliphatic, alicyclic, aromatic orheterocyclic group; R2 represents an aliphatic, alicyclic or aromaticgroup; R3 represents a bifunctional or more organic group selected fromthe group containing a first acid-cleavable group, first base-cleavablegroup or first thermally-cleavable group; R4 represents a monofunctionalhydrophilic group or a monofunctional hydrophilic group protected bysecond acid-cleavable group, second base-cleavable group, orcrosslinkable cleavable group; R5 represents hydrogen or a thirdacid-cleavable group; and h represents an integer of 1 or more. Inparticular, h represents 1 or more and 8 or less in one embodiment; andh represents 1 or more and 4 or less in another embodiment; and hrepresents 1 or 2 in yet another embodiment. Generally, h corresponds tothe number minus 1 of the functionality of R3. The photosensitivecomposition further includes a photosensitive additive.

Since the polyimide precursor can be easily dissolved into a solvent, itbecomes easy to make a varnish solution and to make a relief pattern. Itis not necessary to convert the precursor into a polyimide. R4 and/or R5can change the alkali solubility of the polyimide when thephotosensitive composition is irradiated to actinic light. Thephotosensitive composition of the present invention can be preparedeither as a positive type or a negative type. R3 can be cleaved afterdeveloping a pattern, so that the groups of R3 and R4, which can includea hydrophilic group, can be removed, resulting in improved stability andreliability of the relief pattern.

Examples of the photosensitive additive can include adiazonaphthoquinone compound (DNQ), a photo-acid generator (PAG), aphoto-base generator (PBG), a free radical generator (FRG), andcombinations thereof. The photosensitive additive can differentiate thedissolution rate into a developer solution in order to develop apattern. The photosensitive composition can further include acrosslinker, a thermal acid generator (TAG), and a photosensitizer, ifnecessary.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an IR spectrum of one of the polyimides used in the presentinvention.

FIG. 2 shows the relationship of the dissolution rate versus the amountof photosensitive compound added.

FIG. 3 shows the contrast curve for the polyimide-based photosensitiveformulation.

FIG. 4 shows a SEM picture taken of the developed pattern formed fromthe exposure and development of the photosensitive composition of thepresent invention.

FIG. 5 shows a mass spectrum at 250° C. of the polyimide of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION (A) Polyimide and PolyimidePrecursor

(1) R3

After developing the pattern in the developer solution, the groups of R3and R4 can be removed from the polyimide or the polyimide precursor.Thus, the stability and reliability of the relief pattern are improved.

(i) Examples of R3

As to the polyimide or polyimide precursor, examples of R3 are shown inFormulas 3 through 7, and Formulas 3a through 7a below. These groups canbe incorporated in the polyimide or polyimide precursor by variousmethods.

Among the groups listed below, Formulas 3, 3a, 4, 4a, 5, 5a, 6 and 6acan serve as an acid-cleavable group. These groups can be easily cleavedin the presence of an acid. This group can be cleaved in the presence ofan acid at a temperature between 50 and 180° C. in one embodiment, andat a temperature between 80 and 130° C. in another embodiment.

Among the groups listed below, Formulas 7 and 7a can serve as abase-cleavable group. The group can be easily cleaved at the presence ofa base. This group can be cleaved in the presence of a base at atemperature between 50 and 180° C. in one embodiment, and at atemperature between 80 and 130° C. in another embodiment.

Among the groups listed below, Formulas 3, 3a, 4, 4a, 5, 5a, 6 and 6acan also serve as thermally-cleavable groups. The groups can be easilycleaved at a temperature between 100° C. and 350° C. in one embodiment,and at a temperature between 120° C. and 270° C. in another embodiment.

In Formulas 3 and 3a, A represents R4; R6, R7, R17, and R18 eachrepresents an organic group having a carbon number of 1 to 40; r and qeach represents an integer of 0 or 1; and i represents h which is aninteger of 1 or more. R6, R7, R17, and R18 each can include analiphatic, alicylclic, aromatic or heterocyclic group.

In Formulas 4 and 4a, A represents R4; R8 and R28 each representshydrogen or an organic group having a carbon number of 1 to 40; R9, R19,and R20 each represents an organic group having a carbon number of 1 to40; n, s, and t each represents an integer of 0 or 1; and i represents hwhich is an integer of 1 or more. R8, R9, R19, R20, and R28 each caninclude an aliphatic, alicylclic, aromatic or heterocyclic group.

In Formulas 5 and 5a, A represents R4; R21 and R22 each represents anorganic group having a carbon number of 1 to 40; u and v each representsan integer of 0 or 1; and i represents h which is an integer of 1 ormore. R21 and R22 each can include an aliphatic, alicylclic, aromatic orheterocyclic group.

In Formulas 6 and 6a, A represents R4; R11 and R12 each representshydrogen or an organic group having a carbon number of 1 to 40; R23 andR24 each represents an organic group having a carbon number of 1 to 40;w and x each represents an integer of 0 or 1; and i represents h whichis an integer of 1 or more. R11, R12, R23 and R24 each can include analiphatic, alicylclic, aromatic or heterocyclic group.

In Formulas 7 and 7a, A represents R4; R13, R14 and R15 each representshydrogen or an organic group having a carbon number of 1 to 40; R25 andR26 each represents an organic group having a carbon number of 1 to 40;y and z each represents an integer of 0 or 1; and i represents h whichis an integer of 1 or more. R13, R14, R15, R25, and R26 each can includean aliphatic, alicylclic, aromatic or heterocyclic group.

(2) R4

In order to develop a pattern in a developer solution, the alkalisolubility of the photosensitive composition must be differentiatedbetween the exposed region and the non-exposed region. In the presentinvention, the group represented by R4 of the polyimide or the polyimideprecursor (e.g., polyamic acid) can serve to change the alkalisolubility.

(i) If R4 of Formula 1 is a hydrophilic group, the polyimide orpolyimide precursor, per se, is soluble in an alkali developer solution.When such a polyimide or polyimide precursor coexists with aphotosensitive additive, the alkali solubility of the polyimide orpolyimide precursor can be decreased. Thus, the polyimide or polyimideprecursor is generally insoluble in a developer solution. However, whenirradiated with actinic light, the photosensitive additive is changedinto an alkali soluble group. Thus, the exposed region can be dissolvedin an alkali solution, so that a photosensitive composition can beprovided as a positive material.

(ii) If R4 is a hydrophilic group partially or wholly protected by anacid-cleavable group, the polyimide or polyimide precursor, per se, canbe insoluble in an alkali developer solution. In this case, thephotosensitive composition generally includes a photoacid generator(PAG). When the photosensitive composition is exposed to actinic light,the photoacid generator generates an acid which cleaves theacid-cleavable groups of R4 such that the polyimide or polyimideprecursor becomes soluble in an alkali developer solution. Thus, such aphotosensitive composition can be provided as a positive material.

(iii) If R4 is a hydrophilic group partially or wholly protected by abase-cleavable group, the polyimide or polyimide precursor, per se, canbe insoluble in an alkali solution. In this case, the photosensitivecomposition generally includes a photobase generator (PBG). When thephotosensitive composition is exposed to actinic light, the photobasegenerator generates a base, which cleaves or releases the base-cleavablegroups of R4 such that the polyimide or polyimide precursor becomessoluble in the alkali aqueous solution. Thus, such a photosensitivecomposition can be provided as a positive resist material.

(iv) If R4 is a hydrophilic group partially or wholly protected by acrosslinkable group, the polyimide or polyimide precursor, per se, canbe generally soluble in an alkali solution. In this case, thephotosensitive composition of the present invention generally includes aphotobase generator (PBG), photoacid generator (PAG) or free radicalgenerator (FRG). When it is exposed to actinic light, the PBG generatesa base or the PAG generates an acid or the FRG generates a free radical,which causes crosslinking of the crosslinkable group of the polyimide orpolyimide precursor, such that the polyimide or polyimide precursorbecomes insoluble in the alkali developer solution. Thus, such aphotosensitive composition can be provided as a negative resistmaterial.

According to the present invention, the group represented by R4 canchange the alkali solubility of the photosensitive composition todevelop a pattern. As to the polyimide or polyimide precursor, examplesshown by R4 can include the following groups represented by Formulas 8to 12:

—OR¹⁶  Formula 9—COOR¹⁶  Formula 10—SO₃R¹⁶  Formula 11—NR¹⁶—SO₂CF₃  Formula 12

In the Formulas 8 to 12, R16 represents hydrogen, an acid-cleavablegroup, a base-cleavable group or a crosslinkable group. These groups canbe incorporated in the polyimide or polyimide precursor by variousmethods.

(v) Acid-Cleavable Group

The acid-cleavable group is a group which decreases the alkalisolubility of the polyimide. The acid-cleavable protecting group of thepresent invention when exposed to actinic light is cleaved such that thealkali solubility of the material is recovered. The acid-cleavablegroups included in R4 or R5 can be incorporated by replacing a hydrogenatom of the polyimide or polyimide precursor with a correspondingacid-cleavable group. However, the production method of the polyimide isnot limited thereto, and different processes for obtaining the samerepeating unit can be envisaged to one skilled in the art.

Examples of the acid-cleavable group are alkoxycarbonyl groups, acetalgroups, and silyl groups. Examples of the alkoxycarbonyl groups caninclude tert-butoxycarbonyl group, tert-butoxycarbonyl methyl,tert-amyloxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl groupand i-propoxycarbonyl group. Examples of the acetal groups can includemethoxymethyl group, ethoxyethyl group, methoxy ethoxyethyl, butoxyethylgroup, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethylgroup, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropylgroup, ethoxybutyl group, and ethoxyisobutyl group. Examples of thesilyl groups can include trimethylsilyl group, ethyldimethylsilyl group,methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilylgroup, methyldi-i-propylsilyl group, tri-i-propylsilyl group,t-butyl-dimethylsilyl group, methyl-di-t-butylsilyl group,tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilylgroup and triphenylsilyl group.

(vi) Base-Cleavable Group

The base-cleavable group included in R4 can be partially or whollyincorporated by replacing a hydrogen atom of a polyimide or a polyimideprecursor with a corresponding base-cleavable group. The productionmethod of the polyimide is not limited thereto, and different processesfor obtaining the same repeating unit can be envisaged to one skilled inthe art. The base-cleavable group is a group which decreases the alkalisolubility of the polyimide.

Examples of the base-cleavable group are alkoxycarbonyl groups such as2-cyano-1-methylethoxycarbonyl group, 2,2-dicyano-1-methylethoxycarbonylgroup, 9-fluorenylmethoxycarbonyl groups, 2-methylsulfonylethoxycarbonylgroup, 2-acetyl-1-methylethoxycarbonyl group,2-benzoyl-1-methylethoxycarbonyl group, and2-cyano-2-ethoxycarbonyl-2-methylethoxycarbonyl group.

(vii) Crosslinkable Group

The crosslinkable groups included in R4 can be partially or whollyincorporated by replacing a hydrogen atom of a polyimide or polyimideprecursor with a corresponding crosslinkable group. Generally, thecrosslinkable group can be partially incorporated so as to keep thepolyimide soluble in the alkaline developer solution. The productionmethod of the polyimide is not limited thereto, and different processesfor obtaining the same repeating unit can be envisaged to one skilled inthe art. The crosslinkable groups of the present invention can include acyclic epoxy group, vinyl ether, acrylate, methacrylate, alkoxy methylamino or vinyl group, which can cause crosslinking by the action of thephotosensitive additive of the present invention when irradiated toactinic light.

(3) R1

In preparing the polyimide and polyimide precursor of the presentinvention, various diamines including aliphatic, alicyclic, aromatic orheterocyclic group can be used. These diamines can be copolymerizablewith other diamines. Examples of the useful diamines are1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine,3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl,3,3″-diaminoterphenyl, 4,4″-diaminoterphenyl, oxy-3,3′-dianiline,oxy-4,4′-dianiline, thio-3,3′-dianiline, thio-4,4′-dianiline,sulfonyl-3,3′-dianiline, sulfonyl-4,4′-dianiline,methylene-3,3′-dianiline, methylene-4,4′-dianiline,1,2-ethylene-3,3′-dianiline, 1,2-ethylene-4,4′-dianiline,2,2-propylidene-3,3′-dianiline, 2,2-propylidene-4,4′-dianiline,1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3′-dianiline,1,1,2,2,3,3-hexafluoro-1,3-propylidene-3,3′-dianiline,1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3′-dianiline,1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline,1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene,1,3-bis(3-aminophenylthio)benzene, 1,3-bis(4-aminophenylthio)benzene,1,3-bis(3-aminophenylsulfonyl)benzene,1,3-bis(4-aminophenylsulfonyl)benzene,1,3-bis[2-(3-aminophenyl)-2-propyl]benzene,1,3-bis[2-(4-aminophenyl)-2-propyl]benzene,1,3-bis[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propyl]benzene,1,3-bis[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propyl]benzene,1,4-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene,1,4-bis(3-aminophenylthio)benzene, 1,4-bis(4-aminophenoxy)benzene,1,4-bis(3-aminophenylsulfonyl)benzene,1,4-bis(4-aminophenylsulfonyl)benzene,1,4-bis[2-(4-aminophenyl)-2-propyl]benzene,1,4-bis[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propyl]benzene,1,4-bis[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propyl]benzene,2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane,5-fluoro-1,3-phenylenediamine, 2-fluoro-1,4-phenylenediamine,2,5-fluoro-1,4-phenylenediamine,2,4,5,6-hexafluoro-1,3-phenylenediamine,2,3,5,6-hexafluoro-1,4-phenylenediamine,3,3′-diamino-5,5′-difluorobiphenyl, 4,4′-diamino-3,3′-difluorobiphenyl,3,3′-diamino-2,2′,4,4′,5,5′,6,6′-octafluorobiphenyl,oxy-5,5′-bis(3-fluoroaniline), oxy-4,4′-bis(2-fluoroaniline),oxy-4,4′-bis(3-fluoroaniline), sulfonyl-4,4′-bis(2-fluoroaniline),sulfonyl-4,4′-bis(3-fluoroaniline),1,3-bis(3-amino-5-fluorophenoxy)benzene,1,3-bis(3-amino-5-fluorophenoxy)-5-fluorobenzene,5-(trifluoromethyl)-1,3-phenylenediamine,2-(trifluoromethyl)-1,4-phenylenediamine,2,5-bis(trifluoromethyl)-1,4-phenylenediamine,2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl,3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl,oxy-5,5′-bis[3-(trifluoromethyl)aniline],oxy-4,4′-bis[2-(trifluoromethyl)aniline],oxy-4,4′-bis[3-(trifluoromethyl)aniline],sulfonyl-4,4′-bis[2-(trifluoromethyl)aniline],sulfonyl-4,4′-bis[3-(trifluoromethyl)aniline],1,3-bis(3-aminophenoxy)-5-(trifluoromethyl)benzene,1,3-bis[3-amino-5-(trifluoromethyl)phenoxy]benzene,1,3-bis[3-amino-5-(trifluoromethyl)phenoxy]-5-(trifluoromethyl)benzene,3,3′-bis(trifluoromethyl)-5,5′-diaminobiphenyl,bis(3-aminophenoxy)dimethylsilane,1,3-bis(3-aminophenoxy)-1,1,3,3-tetramethyldisiloxane,1,3-bis(4-aminophenoxy)-1,1,3,3-tetramethyldisiloxane, methanediamine,1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine,1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine,1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine,1,2-bis(3-aminopropoxy)ethane, 1,3-diaminocyclohexane,1,4-diaminecyclohexane, bis(3-aminocyclohexyl)methane,bis(4-aminocyclohexyl)methane, 1,2-bis(3-aminocyclohexyl)ethane,1,2-bis(4-aminocyclohexyl)ethane, 2,2-bis(3-aminocyclohexyl)propane,2,2-bis(4-aminocyclohexyl)propane, bis(3-aminocyclohexyl)ether,bis(4-aminocyclohexyl)ether, bis(3-aminocyclohexyl)sulfone,bis(4-aminocyclohexyl)sulfone,2,2-bis(3-aminocyclohexyl)-1,1,1,3,3,3-hexafluoropropane,2,2-bis(4-aminocyclohexyl)-1,1,1,3,3,3-hexafluoropropane,1,3-xylenediamine, 1,4-xylenediamine, 1,8-diaminonaphathalene,2,7-diaminonaphathalene, 2,6-diaminonaphathalene, 2,5-diaminopyridine,2,6-diaminopyridine, 2,5-diaminopyrazine, and 2,4-diamino-s-triazine.These diamine compounds can be used singly or in combinations of two ormore.

(4) R2

In preparing the polyimide and polyimide precursor of the presentinvention, various tetracarboxylic dianhydrides containing aliphatic,alicyclic, aromatic or heterocyclic groups can be used. Specificexamples of R2 are pyromellitic dianhydride, 3-fluoropyromelliticdianhydride, 3,6-difluoropyromellitic dianhydride,3-(trifluoromethyl)pyromellitic dianhydride,3,6-bis(trifluoromethyl)pyromellitic dianhydride,1,2,3,4-benzentetracarboxylic dianhydride,3,3′,4,4′-benzophenonetetracarboxylic dianhydride,2,2′,3,3′-benzophenonetetracarboxylic dianhydride,3,3′,4,4′-biphenyltetracarboxylic dianhydride,3,3″,4,4″-terphenyltetracarboxylic dianhydride,3,3′″,4,4′″-quaterphenyltetracarboxylic dianhydride,3,3″″,4,4″″-quinoquephenyltetracarboxylic dianhydride,2,2′,3,3′-biphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalicdianhydride, 1,1-ethylidene-4,4′-diphthalic dianhydride,2,2-propylidene-4,4′-diphthalic dianhydride,1,2-ethylene-4,4′-diphthalic dianhydride,1,3-trimethylene-4,4′-diphthalic dianhydride,1,4-tetramethylene-4,4′-diphthalic dianhydride,1,5-pentamethylene-4,4′-diphthalic dianhydride,1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride,difluoromethylene-4,4′-diphthalic dianhydride,1,1,2,2-tetrafluoro-1,2-ethylene-4,4′-diphthalic dianhydride,1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4′-diphthalic dianhydride,1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalicdianhydride,1,1,2,2,3,3,4,4,5,5-decafluoro-1,3-trimethylene-4,4′-diphthalicdianhydride, oxy-4,4′-diphthalic dianhydride, thio-4,4′-diphthalicdianhydride, sulfonyl-4,4′-diphthalic dianhydride,1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethylsiloxane dianhydride,1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride,1,4-bis(3,4-dicarboxyphenyl)benzene dianhydride,1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride,1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride,1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride,1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride,bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride,bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride,2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride,2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropanedianhydride,2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropanedianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride,1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride,2,3,6,7-naphthalenetetracarboxylic dianhydride,1,4,5,8-naphthalenetetracarboxylic dianhydride,1,2,5,6-naphthalenetetracarboxylic dianhydride,3,4,9,10-perylenetetracarboxylic dianhydride,2,3,6,7-anthracenetetracarboxylic dianhydride,1,2,7,8-phenanthrenetetracarboxylic dianhydride,1,3-bis(3,4-dicarboxyphenoxy)-1,1,3,3-tetramethyldisiloxane dianhydride,ethylenetetracarboxylic dianhydride, cyclopentanetetracarboxylicdianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride,cyclohexane-1,2,4,5-tetracarboxylic dianhydride,3,3′,4,4′-bicyclohexyltetracarboxylic dianhydride,carbonyl-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,methylene-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,1,2-ethylene-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,1,1-ethylidene-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,2,2-propylidene-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,oxy-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,thio-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,sulfonyl-4,4′-bis(cyclohexane-1,2-dicarboxylic)dianhydride,2,2′-difluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride,5,5′-difluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride,6,6′-difluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2′,5,5′,6,6′-hexafluoro-3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2′-bis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride,5,5′-bis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride,6,6′-bis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride,2,2′,5,5′-tetrakis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylicdianhydride,2,2′,6,6′-tetrakis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylicdianhydride,5,5′,6,6′-tetrakis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylicdianhydride,2,2′,5,5′,6,6′-hexakis(trifluoromethyl)-3,3′,4,4′-biphenyltetracarboxylicdianhydride, 3,3′-difluoro-oxy-4,4′-diphathalic dianhydride,5,5′-difluoro-oxy-4,4′-diphathalic dianhydride,6,6′-difluoro-oxy-4,4′-diphathalic dianhydride,3,3′,5,5′,6,6′-hexafluoro-oxy-4,4′-diphathalic dianhydride,3,3′-bis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,5,5′-bis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,6,6′-bis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,3,3′,5,5′-tetrakis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,3,3′,6,6′-tetrakis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,5,5′,6,6′-tetrakis(trifluoromethyl)-oxy-4,4′-diphathalic dianhydride,3,3′,5,5′,6,6′-hexakis(trifluoromethyl)-oxy-4,4′-diphathalicdianhydride, 3,3′-difluoro-sulfonyl-4,4-diphathalic dianhydride,5,5′-difluoro-sulfonyl-4,4-diphathalic dianhydride,6,6′-difluoro-sulfonyl-4,4-diphathalic dianhydride,3,3′,5,5′,6,6′-hexafluoro-sulfonyl-4,4-diphathalic dianhydride,3,3′-bis(trifluoromethyl)-sulfonyl-4,4-diphathalic dianhydride,5,5′-bis(trifluoromethyl)-sulfonyl-4,4-diphathalic dianhydride,6,6′-bis(trifluoromethyl)-sulfonyl-4,4-diphathalic dianhydride,3,3′,5,5′-tetrakis(trifluoromethyl)-sulfonyl-4,4-diphathalicdianhydride,3,3′,6,6′-tetrakis(trifluoromethyl)-sulfonyl-4,4-diphathalicdianhydride,5,5′,6,6′-tetrakis(trifluoromethyl)-sulfonyl-4,4-diphathalicdianhydride,3,3′,5,5′,6,6′-hexakis(trifluoromethyl)-sulfonyl-4,4-diphathalicdianhydride, 3,3′-difluoro-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride, 5,5′-difluoro-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride, 6,6′-difluoro-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,3,3′,5,5′,6,6′-hexafluoro-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,3,3′-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,5,5′-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,6,6′-bis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,3,3′,5,5′-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,3,3′,6,6′-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,5,5′,6,6′-tetrakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,3,3′,5,5′,6,6′-hexakis(trifluoromethyl)-2,2-perfluoropropylidene-4,4′-diphathalicdianhydride,9-phenyl-9-(trifluorophenyl)xanthene-2,3,6,7-tetracarboxylicdianhydride, 9,9-bis(trifluorophenyl)xanthene-2,3,6,7-tetracarboxylicdianhydride, and bicyclo[2,2,2]oct-7-ene-2,3,6,7-tetracarboxylicdianhydride. These tetracarbocylic dianhydrides can be used singly or incombination of two or more.

(5) Specific Examples of the Polyimide and Polyimide Precursor

(i) In Formula 1 or 2, one example of the polyimide or polyimideprecursor has an organic group represented by Formula 13 as R1, anorganic group represented by Formula 14 as R3 wherein A represents R4,and an organic group represented by Formula 8 as R4:

In Formula 14, m represents h which is an integer of 1, 2, 3, 4 or 5.

(ii) In Formula 1 or 2, another example of the polyimide or polyimideprecursor has an organic group represented by Formula 13 as R1, anorganic group represented by Formula 15 as R3 wherein D represents R4,and an organic group represented by Formula 8 as R4:

In Formula 15, o represents h which is an integer of 1, 2, 3, 4 or 5.

(iii) In Formula 1 or 2, another example of the polyimide or polyimideprecursor has an organic group represented by Formula 13 as R1, anorganic group represented by Formula 16 as R3 wherein E represents R4,and an organic group represented by Formula 8 as R4:

In Formula 16, p represents h which is an integer of 1, 2, 3, 4 or 5.

(iv) Specifically, the polyimide as represented by the Formula 17 can beused as one embodiment of the present invention.

In Formula 17, R16 and R27 independently represent hydrogen, anacid-cleavable group, a base-cleavable group or a crosslinkable group.

The polyimide as represented by Formula 17, per se, is soluble orinsoluble in a developer solution, depending on the structures of R16and R27. However, the alkali solubility of the polyimide is changed whenthe photosensitive composition is exposed to actinic light. Thecomposition of the present invention can be used as a positive ornegative resist material.

(i) In case where at least one of R16 and R27 of the polyimide ishydrogen, the polyimide as represented by Formula 17, per se, isgenerally soluble in an alkali developer solution. The hydroxyl group ofthe hexafluoroisopropanol groups is a moiety which imparts solubility inalkali solution. Such a polyimide can be prepared, for example, throughthe Production Examples 1 to 8 as described later. However, theproduction method of the polyimide is not limited thereto.

When such a polyimide coexists with a photosensitive additive, thealkali solubility of the polyimide can be decreased. Therefore, thepolyimide is insoluble in a developer solution. However, when irradiatedwith actinic light, the photosensitive additive is changed, and theexposed region can be dissolved in an alkali solution, so that such aphotosensitive composition can be provided as a positive resistmaterial.

(ii) In case where at least one of R16 and R27 of the polyimide is anacid-cleavable group, the polyimide as represented by Formula 17, perse, is generally insoluble in an alkali solution. In this case, thephotosensitive composition of the present invention generally includes aphotoacid generator (PAG). When the photosensitive composition isexposed to actinic light, the photoacid generator generates an acid,which cleaves the acid-cleavable groups such that the polyimide becomessoluble in the alkali solution. Thus, such a photosensitive compositioncan be provided as a positive resist material.

(iii) When at least one of R16 and R27 of the polyimide is thebase-cleavable group, the polyimide as represented by Formula 17, perse, is generally insoluble in an alkali solution. In this case, thephotosensitive composition of the present invention generally includes aphotobase generator (PBG). When the photosensitive composition isexposed to actinic light, the photobase generator generates a base,which cleaves the base-cleavable groups such that the polyimide becomessoluble in the alkali aqueous solution. Thus, such a photosensitivecomposition can be provided as a positive resist material.

(iv) When at least one of R16 and R27 of the polyimide is acrosslinkable group, the polyimide as represented by formula 17, per se,is generally soluble in an alkali solution. In this case, thephotosensitive composition generally includes a photobase generator(PBG), photoacid generator (PAG), or free radical generator (FRG). Whenit is exposed to actinic light, the PBG generates a base, the PAGgenerates an acid, and the FRG generates a free radical which causescrosslinking of the crosslinkable group of the polyimide, such that thepolyimide becomes insoluble to the alkali solution. Thus, such aphotosensitive composition can be provided as a negative resistmaterial.

(v) R16 and R27 independently represent hydrogen, an acid-cleavablegroup, a base-cleavable group and a crosslinkable group. R16 can bedifferent from R27. In such a case, the alkali solubility of thepolyimide as represented by formula 17 depends on the interactionbetween the polyimide and the photosensitive additive, and the affinityof the polyimide to the developer solution.

(B) Photosensitive Additives

As explained above, the photosensitive composition of the presentinvention includes a photosensitive additive. According to the presentinvention, any photosensitive additives can be used which decrease orincrease the solubility of the polyimide or polyimide precursor suchthat the alkali solubility of the exposed region is differentiated fromthat of the non-exposed region so as to develop an appropriate pattern.

Depending on the groups of R3, R4 and R5, one or more photosensitiveadditives can be used such that the alkali solubility of the polyimideand polyimide precursor can be changed by the actinic light irradiation.Generally, distinct photosensitive additives have different absorptionwavelengths. Therefore, by using distinct actinic lights correspondingto the photosensitive additives, a pattern can be formed by distinctstages.

Such photosensitive additives can be (i) one which suppresses the alkalisolubility of the polyimide or polyimide precursor; (ii) a photoacidgenerator (PAG); (iii) a free radical generator (FRG); and (iv) aphotobase generator (PBG).

(i) Photosensitive Additive which Suppresses the Alkali Solubility ofthe Polyimide or Polyimide Precursor

Generally, the photosensitive additive suppresses the alkali solubilityof the polyimide or polyimide precursor. Examples thereof are compoundssuch as diazonium salts, diazoquinone sulphonamides, diazoquinonesulphonic acid esters, diazoquinone sulphonates, nitrobenzyl esters,onium salts, halides, halogenated isocyanates, triazine halides,bisarylsulphonyldiazomethanes, disulphones and the like. In particular,o-diazoquinone (o-quinone diazides), and more in particular,o-diazonaphthoquinones (DNQ, o-naphthoquinone diazides) can be generallyused, because these compounds are effective in suppressing alkalisolubility. However, when actinic light is irradiated, an alkali solublemoiety is formed. Therefore, the exposed region becomes soluble in analkali solution, whereas the non-exposed region is still insoluble inthe alkali solution.

The o-diazoquinones (o-quinone diazides) can be obtained, for example,by condensation reaction of an o-quinonediazide sulphonyl chloride witha polyhydroxy compound, a polyamine compound or a polyhydroxy polyaminecompound.

The o-Quinonediazide sulphonyl chlorides can include1,2-benzoquinone-2-azido-4-sulphonyl chloride,1,2-naphthoquinone-2-diazido-5-sulphonyl chloride,1,2-naphthoquinone-2-diazido-6-sulphonyl chloride and1,2-naphthoquinone-2-diazido-4-sulphonyl chloride.

The polyhydroxy compounds can include hydroquinone, resorcinol,pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane,2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxybenzophenone,2,3,4-trihydroxy diphenyl methane, 2,3,4,4′-tetrahydroxy diphenylmethane 2,3,4,4′-tetrahydroxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone, tris(4-hydroxyphenyl)methane,1,1,1-tris(4-hydroxyphenyl)ethane,1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene,1-naphthol, 2-naphthol, methyl gallate and ethyl gallate.

The polyamine compounds can include 1,4-phenylenediamine,1,3-phenylenediamine, 4,4′-diaminodiphenyl ether,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulphone and4,4′-diaminodiphenylsulphide.

The polyhydroxy polyamine compounds can include2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and3,3-dihydroxybenzidine.

Specific examples of the o-diazoquinones are1,2-benzoquinone-2-azido-4-sulphonate ester or sulphonamide,1,2-naphthoquinone-2-diazido-5-sulphonate ester or sulphonamide, and1,2-naphthoquinone-2-diazido-4-sulphonate ester or sulphonamide.

The photosensitive additive (i) can be included in the photosensitivecomposition of the present invention at an amount of 0.01 to 40 wt %with respect to total solids in one embodiment, or at an amount of 5 to30 wt % with respect to total solids in another embodiment, or at anamount of 15 to 25 wt % with respect to total solids in yet anotherembodiment.

(ii) Photoacid Generator (PAG)

In the present invention, the photoacid generator generates an acid whenit is exposed to actinic light. The photoacid generator useful in thepresent invention can be onium salts, sulfonate ester, ordisulfonyldiazomethanes. These photoacid generators can be includedalone or in combination thereof. The photoacid generator can be includedin the photosensitive composition of the present invention at an amountof 0.01 to 20 wt % with respect to total solids in one embodiment, or atan amount of 1 to 10 wt % with respect to total solids in anotherembodiment, or at an amount of 3 to 7 wt % with respect to total solidsin yet another embodiment.

(iii) Photobase Generator (PBG)

In the present invention, the photobase generator generates a base whenit is exposed to actinic light. The examples of the photobase generatorare cobalt amine complexes as represented by Co(III)(RNH₂)₅X²⁺, whereinR represents hydrogen or an alkyl group having a carbon number of 1 ormore, and X represents Br⁻ and Cr⁻. Other examples of the photobasegenerators are oxime esters, carbamic acids, nitrobenzyl sulfonamides,and quaternary ammonium salts but not to be limited thereto. Thesephotobase generators can be included alone or in combination thereof.The photobase generator can be included in the photosensitivecomposition of the present invention at an amount of 0.01 to 20 wt %with respect to total solids in one embodiment, or at an amount of 1 to10 wt % in another embodiment, or at an amount of 3 to 7 wt % withrespect to total solids in yet another embodiment.

(iv) Free Radical Generator (FRG)

The free radical generator generates a radical when it is exposed toactinic light. The examples of the free radical generators are benzoinethers, benzyl derivatives, trichlorotriazines, and phosphine oxides,but not to be limited thereto. These free radical generators can beincluded alone or in combination thereof. The free radical generator canbe included in the photosensitive composition of the present inventionat an amount of 0.01 to 20 wt % with respect to total solids in oneembodiment, or at an amount of 1 to 10 wt % with respect to total solidsin another embodiment, or at an amount of 3 to 7 wt % with respect tototal solids in yet another embodiment.

(C) Photosensitizer

A photosensitizer can be further included in the photosensitivecomposition of the present invention. If the photosensitive compositionas prepared is transparent to the wavelength of the actinic light, aphotosensitizer is useful. The photosensitizer can receive the energy ofthe actinic light, which can be transferred to the photosensitiveadditive of the present invention. Thus, using the photosensitizerenhances the choice of the photosensitive additives which can be used inthe present invention. Examples of the photosensitizer are aromaticcompounds such as naphthalenes, anthracenes and pyrenes; carbazolederivatives, aromatic carbonyl compounds, benzophenone derivatives,thioxanthone derivatives and coumarin derivatives. In particular,specific examples of the photosensitizers are 1-methylnaphthalene,2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene,2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene,1-iodinenaphthalene, 2-iodinenaphthalene, 1-naphthol, 2-naphthol,1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene,anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene,9,10-dibromoanthracene, 9,10-diphenyl anthracene, 9-cyanoanthracene,9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, carbazole,9-methylcarbazole, 9-phenylcarbazole, 9-propyl-9H-carbazole,9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H-carbazole,9-methyl-3,6-dinitro-9H-carbazole, 9-carbazole methanol, 9-carbazolepropionic acid, 9-decyl-3,6-dinitro-9H-carbazole,9-ethyl-3,6-dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole,9-ethylcarbazole, 9-isopropylcarbazole,9-(ethoxycarbonylmethyl)carbazole, 9-(morpholinomethyl)carbazole,9-acetylcarbazole, 9-arylcarbazole, 9-benzyl-9Hcarbazole, 9-carbazoleacetic acid, 9-(2-nitrophenyl) carbazole, 9-(4-methoxyphenyl)carbazole,9-(1-ethoxy-2-methyl-propyl)-9H-carbazole, 3-nitrocarbazole,4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole,2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, benzophenone,4-phenylbenzophenone, 4,4′-bis(dimethoxy)benzophenone,4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 2-benzoylbenzoic acid methyl ester, 2-methylbenzophenone,3-methylbenzophenone, 4-methylbenzophenone,3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone,[4-(4-methylphenylthio)phenyl]-phenylmethanone, xanthone, thioxanthone,2-chlorothioxanthone, 4-chloro thioxanthone, 2-isopropyl thioxanthone,4-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethylthioxanthone and 1-chloro-4-propoxy thioxanthone. The photosensitizercan be included alone or in combination thereof. The photosensitizer canbe included at an amount of 0.01 to 20 wt % with respect to total solidsin one embodiment, or at an amount of 0.1 to 10 wt % with respect tototal solids in another embodiment.

(D) Thermal Acid Generator (TAG)

The thermal acid generator generates an acid when it is exposed to heat.According to the present invention, the thermal acid generator (TAG)substantially does not generate an acid when it is exposed to a light.After development of the image, it is heated and the TAG generates acidwhich in turn assists in the cleavage of the acid-cleavable group.Examples of the thermal acid generator are halogenoid nitrogencontaining compounds which generate a halogen radical when being exposedto an infrared light and sulfonate esters including nitrobenzylsulfonates, but not to be limited thereto. These thermal acid generatorscan be included alone or in combination thereof. The thermal acidgenerator can be included in the photosensitive composition of thepresent invention at an amount of 0.01 to 20 wt % with respect to totalsolids in one embodiment, or at an amount of 1 to 10 wt % with respectto total solids in another embodiment, or at an amount of 3 to 7 wt %with respect to total solids in yet another embodiment.

(E) Crosslinker

A crosslinker can be further added to the photosensitive composition ofthe present invention. The crosslinker causes crosslinking reaction suchthat the exposed region becomes insoluble in the alkali solution. Whenthe acid-cleavable group, base-cleavable group, thermal cleavable groupand/or hydrophilic group remain after forming the relief pattern, thecrosslinker can be useful because the crosslinker can react with thesegroups. The reaction by the crosslinker can modify the properties of therelief pattern, such as tensile strength thereof. For example, if ahydrophilic group such as hydroxyl group or carboxyl group is generatedat the portion where R3 is cleaved off, the crosslinker can react withthe generated hydrophilic group, so as to cause the crosslinkingreaction. The crosslinker can include compounds which have two or moreepoxy groups, vinyl ether groups, acrylate, methacrylate, methylolgroups or alkoxymethyl groups. Examples of the crosslinkers arebisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AD epoxyresins, cresol novolac epoxy resins, phenol novolac epoxy resins,glycidyl amine epoxy resins, polysulfide epoxy resins, dimethylol ureas,alkoxy methyl melamines and so on. According to the present invention,the crosslinker means a compound which is different from thecrosslinkable group included in the polyimide as mentioned above. Thecrosslinker can be added into the photosensitive composition. Thecrosslinker can be included at an amount of 0.01 to 40 wt % with respectto total solids in one embodiment, or at an amount of 0.1 to 20 wt %with respect to total solids in another embodiment, in thephotosensitive composition.

(F) Solvent

A solvent can be added in order to dissolve or homogenously dispersesthe components of the present invention. Specific examples of thesolvents are propylene glycol methylether acetate,N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulphoxide, 1,3-dimethylimidazolidinone, hexamethylphosphoramideand γ-butyrolactone. Other solvents such as isopropanol, ethanol,methanol, water, tetrahydrofuran, propylene glycol monomethyl etheracetate, propylene glycol monomethyl ether, ethyl lactate and diethyladipate can be also used. The solvents as mentioned above can be usedalone or in combinations.

(G) Method

(i) Forming Pattern

Using the photosensitive composition of the present invention, a reliefpattern can be formed as follows. First, the photosensitive compositionis applied onto a substrate of e.g., a silicon wafer, a ceramic orgallium arsenide. The photosensitive composition can be applied by usinga spinner, spray application or roller coating. Generally, thephotosensitive composition is applied such that the photosensitivecomposition film after being dried has a thickness from 0.1 μm to 150μm. The drying process can be generally carried out at a temperature of50° C. to 150° C. for a period of 1 minute to several hours.

Then, the photosensitive composition film is exposed to actinic lightradiation. Upon irradiation, a mask with desired patterns can be used.Use of a laser beam via a direct write process can eliminate the processof applying the mask. By exposing the photosensitive composition film toactinic light, the alkali solubility of the polyimide or polyimideprecursor can be differentiated between the exposed portion and thenon-exposed portion. Generally, an actinic light can be selected whichhas a wavelength sensitive to the photosensitive additive. Examples ofthe actinic lights are ultraviolet light, far ultraviolet light,infrared light, an electron beam, X-rays and the like. For example, KrFline (248 nm), 1-line (365 nm), h-line (405 nm) and g-line (436 nm) canbe used.

In the case of a positive-acting composition, after the irradiation, theexposed regions are removed by dissolving them in an alkaline solution,that is, a developer solution. In the case of a negative-actingcomposition, after the irradiation, the non-exposed regions are removedby dissolving them in an alkaline solution. The developer solution canbe an alkali solution or alkali aqueous solution which includes a basecomponent such astetramethylammonium hydroxide (TMAH), diethanolamine,diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, triethylamine, diethylamine,methylamine, dimethyl amine, dimethylaminoethyl acetate,dimethylaminoethanol, cyclohexylamine, ethylenediamine andhexamethylenediamine. If necessary, the developer solution can furtherinclude polar solvents such as N-methyl-2-pyrrolidone,N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulphoxide,γ-butyrolactone and dimethylacrylamide; alcohols such as methanol,ethanol and isopropanol; esters such as ethyl lactate and propyleneglycol monomethyl ether acetate; and ketones such as cyclopentanone,cyclohexanone, isobutyl ketone and methyl isobutyl ketone. Thesesolvents can be added alone or in combination thereof. Afterdevelopment, the developed pattern is generally rinsed with water.

(ii) Thermal Process

(a) Polyimide

Then, the developed pattern including a polyimide is subjected to athermal process. The polyimide includes an acid-cleavable group or athermally cleavable group as R3, so that the groups of R3 and R4 can beremoved after developing the pattern. The temperature of the thermalprocess depends on the feature of the group R3, and the presence ofthermal acid generator.

The polyimide containing an acid-cleavable pendant group as R3 and TAGare included in the developed pattern, R3 can be cleaved at atemperature between 50 and 180° C. in one embodiment, and at atemperature between 80 and 130° C. in another embodiment. If thepolyimide contains a thermally-cleavable group as R3, R3 can be cleavedat a temperature between 100 and 350° C. in one embodiment, and at atemperature between 120 and 270° C. in another embodiment.

(b) Polyimide Precursor

Unlike using the polyimide, the developed pattern containing a polyimideprecursor is subjected to another thermal process. The polyimideprecursor is heated at a temperature of 320 to 350° C. to converting thepolyamic acid into a polyimide. If the polyimide precursor contains athermally cleavable group as R3, it can be cleaved at the same time ofthis conversion. If the polyimide precursor includes an acid-cleavablegroup, some of the groups can be cleaved at the time of the converting.The acid-cleavable group, R3, can also be cleaved by the action of anacid or base, at a different stage from this conversion.

(H) Various Embodiments of Photosensitive Compositions

In accordance with the present invention, various embodiments of thephotosensitive composition can be provided depending on the use.Examples of the present invention are described in Tables 1 and 2.

Embodiment No. 1 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic group; and adiazonaphthoquinone, which can be patternable by using I line(wavelength: 365 nm) or KrF (wavelength: 248 nm.

Embodiment No. 2 includes a polyimide represented by Formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group; adiazonaphthoquinone and PAG. The diazonaphthoquinone decreases thealkali solubility, which can be patternable by I line. After developinga pattern, it can be irradiated a second time to cause the PAG togenerate an acid so as to cleave R3.

Embodiment No. 3 includes a polyimide represented by Formula 1 whereinR3 is a base-cleavable group and R4 is a hydrophilic group. It alsoincludes a diazonaphthoquinone (DNQ) and PBG. The DNQ decreases thealkali solubility, which can be patternable by I line. After developinga pattern, it can be irradiated a second time to cause the PBG togenerate a base so as to cleave R3.

Embodiment No. 4 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by an acid-cleavable group. It alsoincludes a PAG, and it can include a photosensitizer, if necessary. Thepolyimide is insoluble to a developer solution, but when I line or KrFline is irradiated, the exposed region can be soluble by the action ofPAG. The developed pattern is heated to cleave the thermally-cleavablegroup of R3.

Embodiment No. 5 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group. It also includesa PBG, and it can include a crosslinker and a photosensitizer, ifnecessary. The polyimide is soluble to a developer solution, but byirradiating I line or KrF line, the exposed region can become insolubleby causing the crosslinking of the polymer. After developing a pattern,it can be heated to cleave the thermally-cleavable group of R3, ifnecessary. The thermally-cleavable group of R3 can remain in the reliefpattern.

Embodiment No. 6 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group. It also includesa PAG, and it can include a crosslinker and a photosensitizer, ifnecessary. The polyimide is soluble to a developer solution, but byirradiating I-line or KrF-line, the exposed region can become insolubleby causing the crosslinking of the polymer. After developing a pattern,it can be heated to cleave the thermally-cleavable group of R3, ifnecessary. The thermally-cleavable group of R3 can remain in the reliefpattern.

Embodiment No. 7 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by a base-cleavable group. It alsoincludes a PBG, and it can include a crosslinker and a photosensitizer,if necessary. The polyimide is insoluble in a developer solution, but byirradiating I-line or KrF-line, the exposed region can be solubilized bythe action of the PBG. After developing a pattern, it is heated so as tocleave the thermally-cleavable group of R3.

Embodiment No. 8 includes a polyimide represented by Formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group. It alsoincludes a DNQ and TAG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide is insoluble to a developersolution, but by irradiating I-line or KrF-line, the exposed region canbecome soluble by the action of DNQ. The developed relief pattern isheated to cleave the acid-cleavable group of R3 by the action of TAG.

Embodiment No. 9 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by an acid-cleavable group. It alsoincludes a PBG and TAG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide is insoluble to a developersolution. By irradiating I-line or KrF-line, the PBG in the exposedregion generates a base, which is then quenched by an acid generatedthere from the TAG upon heating. In the non-exposed region, the acidgenerated from the TAG upon heating cleaves the acid-cleavable group ofR4. After developing a pattern, the thermally cleavable group can becleaved, if necessary.

Embodiment No. 10 includes a polyimide represented by formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group partially orwholly protected by a crosslinkable group. It also includes a PBG andTAG, and it can include a crosslinker and a photosensitizer, ifnecessary. The polyimide is soluble to a developer solution. Byirradiating I-line or KrF-line, the PBG in the exposed region generatesa base, which is then quenched by an acid generated there from the TAGupon heating. In the non-exposed region, the acid generated from the TAGupon heating causes crosslinking. The developed pattern can be heated tocleave the acid-cleavable group of R3, if necessary. The acid-cleavablegroup of R3 can remain in the relief pattern.

Embodiment No. 11 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group. It also includesa PBG and TAG, and it can include a crosslinker and a photosensitizer,if necessary. The polyimide is soluble to a developer solution. Byirradiating I-line or KrF-line, the PBG in the exposed region generatesa base, which is then quenched by the acid generated there from the TAG.In the non-exposed region, the acid generated from the TAG upon heatingcauses crosslinking. The developed pattern can be heated to cleave thethermally-cleavable group of R3, if necessary. The thermally-cleavablegroup of R3 can remain in the relief pattern.

Embodiment No. 12 includes a polyimide represented by Formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group. It alsoincludes a PAG, and it can include a photosensitizer, if necessary. Thepolyimide is soluble to a developer solution. By irradiating I-line orKrF-line, the exposed region is rendered insoluble in a developersolution. The developed pattern can be heated to cleave theacid-cleavable group of R3, if necessary. The acid-cleavable group of R3can remain in the relief pattern.

Embodiment No. 13 includes a polyimide represented by Formula 1 whereinR3 is a base-cleavable group and R4 is a hydrophilic group. It alsoincludes a PBG, and it can include a photosensitizer, if necessary. Thepolyimide is soluble in a developer solution. By irradiating I-line orKrF-line, the exposed region is rendered insoluble in a developersolution. The developed pattern can be heated to cleave thebase-cleavable group of R3, if necessary. The base-cleavable group of R3can remain in the relief pattern.

Embodiment No. 14 includes a polyimide represented by Formula 1 whereinR3 is a thermally-cleavable group and R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group. It also includesan FRG, and it can include a photosensitizer, if necessary. Thepolyimide is soluble in a developer solution. By irradiating I-line orKrF-line, the exposed region can become insoluble by causing thecrosslinking of the polymer. The developed pattern can be heated tocleave the thermally-cleavable group of R3, if necessary. Thethermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 15 includes a polyimide represented by Formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group partially orwholly protected by a crosslinkable group. It also includes an FRG and aTAG, and it can include a photosensitizer, if necessary. The polyimideis soluble in a developer solution. By irradiating I-line or KrF-line,the exposed region can become insoluble by causing the crosslinking ofthe polymer. The developed pattern can be heated to cleave theacid-cleavable group of R3, if necessary. The acid-cleavable group of R3can remain in the relief pattern.

Embodiment No. 16 includes a polyimide represented by Formula 1 whereinR3 is an acid-cleavable group and R4 is a hydrophilic group partially orwholly protected by a base-cleavable group. It also includes a PBG andTAG, and it can include a crosslinker and a photosensitizer, ifnecessary. The polyimide is insoluble in a developer solution, but byirradiating I-line or KrF-line, the exposed region can be solubilized bythe action of the PBG. After developing a pattern, it is heated so as tocleave the acid-cleavable group of R3.

TABLE 1 Photosensitive composition Polyimide represented by Formula 1 R4hydrophilic hydrophilic group group hydrophilic R3 protected byprotected by group Acid- base- thermally- acid- base- protected by Expo-cleavable cleavable cleavable hydrophilic cleavable cleavablecrosslinkable Active sure Positive/ No. group group group group groupgroup group Compound⁽¹⁾ light⁽²⁾ Negative⁽³⁾ 1 x x DNQ I or KrF p 2 X xDNQ + PAG I + KrF p 3 x x DNQ + PBG I + KrF p 4 x x PAG I or KrF p 5 x xPBG I or KrF n 6 x x PAG I or KrF n 7 x x PBG I or KrF p 8 X x DNQ + TAGI or KrF p 9 x x PBG + TAG I or KrF n 10 X x PBG + TAG I or KrF p 11 x xPBG + TAG I or KrF p 12 x x PAG I or KrF n 13 x x PBG I or KrF n 14 x xFRG I or KrF n 15 x x FRG + TAG I or KrF n 16 x x PBG + TAG I or KrF p⁽¹⁾DNQ represents a diazonaphthoquinone compound, PAG represents aphoto-acid generator, PBG represents a photo-base generator, TAGrepresents a thermal acid generator, FRG represents a free radicalgenerator. ⁽²⁾I represents an actinic light having wavelength of 365 nm,KrF represents an actinic light having wavelength of 248 nm.⁽³⁾Lower-case letter p represents a positive-acting composition, andlower-case letter n represents a negative-acting composition.

Table 2 shows various embodiments using the polyimide precursor of thepresent invention.

Embodiment No. 17 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is a thermally-cleavable group,and R5 is an acid-cleavable group. It also includes a DNQ, and it caninclude a crosslinker and a photosensitizer, if necessary. Thecomposition can be patterned by irradiating I-line or KrF-line. Thedeveloped pattern can be heated to cleave the thermally-cleavable groupof R3, if necessary. The thermally-cleavable group of R3 can remain inthe relief pattern.

Embodiment No. 18 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is an acid-cleavable group, andR5 is an acid-cleavable group. It also includes a DNQ and PAG, and itcan include a crosslinker and a photosensitizer, if necessary. The DNQdecreases the alkali solubility of the polyimide precursor, and can bepatterned by I-line irradiation. The developed pattern can be heated tocleave the acid-cleavable group of R3, if necessary. After developing apattern, it can be irradiated a second time to cause the PAG to generatean acid so as to cleave R3.

Embodiment No. 19 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is a base-cleavable group, andR5 is an acid-cleavable group. It also includes a DNQ and PBG, and itcan include a crosslinker and a photosensitizer, if necessary. The DNQdecreases the alkali solubility of the polyimide precursor, and can bepatterned by I-line irradiation. The developed pattern can be heated tocleave the base-cleavable group of R3, if necessary. After developing apattern, it can be irradiated a second time to cause the PBG to generatea base so as to cleave R3.

Embodiment No. 20 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by anacid cleavable group, R3 is a thermally-cleavable group, and R5 is anacid-cleavable group. It also includes a PAG, and it can include acrosslinker and a photosensitizer, if necessary. The composition can bepatterned by irradiating I-line or KrF-line. The developed pattern canbe heated to cleave the thermally-cleavable group of R3, if necessary.The thermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 21 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by abase cleavable group, R3 is a thermally-cleavable group, and R5 is anacid-cleavable group. It also includes a PBG, and it can include acrosslinker and a photosensitizer, if necessary. The composition can bepatterned by irradiating I-line or KrF-line. The developed pattern canbe heated to cleave the thermally-cleavable group of R3, if necessary.The thermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 22 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is an acid-cleavable group, andR5 is an acid-cleavable group. It also includes DNQ and TAG and it caninclude a crosslinker and a photosensitizer, if necessary. The DNQdecreases the alkali solubility of the polyimide precursor, and can bepatterned by I-line or KrF-line irradiation. The developed pattern canbe heated to cleave the acid-cleavable group of R3 by action of the TAG.

Embodiment No. 23 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by aacid cleavable group, R3 is a thermally-cleavable group, and R5 is anacid-cleavable group. It also includes a PBG and TAG, and it can includea crosslinker and a photosensitizer, if necessary. The polyimideprecursor is insoluble to a developer solution. By irradiating I-line orKrF-line, the PBG in the exposed region generates a base, which is thenquenched by an acid generated there from the TAG upon heating. In thenon-exposed region, the acid generated from the TAG upon heating cleavesthe acid-cleavable group of R4. After developing a pattern, thethermally cleavable group of R3 can be cleaved, if necessary.

Embodiment No. 24 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes a PBG and TAG, and it can includea crosslinker and a photosensitizer, if necessary. The polyimideprecursor is soluble to a developer solution. By irradiating I-line orKrF-line, the PBG in the exposed region generates a base, which is thenquenched by the acid from the TAG upon heating. In the non-exposedregion, the acid generated from the TAG upon heating causescrosslinking. The developed pattern can be heated to cleave thethermally-cleavable group of R3, if necessary. The thermally-cleavablegroup of R3 can remain in the relief pattern.

Embodiment No. 25 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes a FRG, and it can include aphotosensitizer, if necessary. The polyimide precursor is soluble in adeveloper solution. By irradiating I-line or KrF-line, the exposedregion can become insoluble by causing the crosslinking of the polymer.The developed pattern can be heated to cleave the thermally-cleavablegroup of R3, if necessary. The thermally-cleavable group of R3 canremain in the relief pattern.

Embodiment No. 26 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes an FRG and a TAG, and it caninclude a photosensitizer, if necessary. The polyimide precursor issoluble in a developer solution. By irradiating I-line or KrF-line, theexposed region can become insoluble by causing the crosslinking of thepolymer. The developed pattern can be heated to cleave theacid-cleavable group of R3 by action of the TAG, if necessary. Theacid-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 27 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes a PAG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursoris soluble to a developer solution, but by irradiating I line or KrFline, the exposed region can become insoluble by causing thecrosslinking of the polymer. After developing a pattern, it can beheated to cleave the thermally-cleavable group of R3, if necessary. Thethermally-cleavable group of R3 can also remain in the relief pattern.

Embodiment No. 28 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes a PBG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursoris soluble to a developer solution, but by irradiating I-line orKrF-line, the exposed region can become insoluble by causing thecrosslinking of the polymer. After developing a pattern, it can beheated to cleave the thermally-cleavable group of R3, if necessary. Thethermally-cleavable group of R3 can also remain in the relief pattern.

Embodiment No. 29 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 is anacid-cleavable group. It also includes a PBG and TAG, and it can includea crosslinker and a photosensitizer, if necessary. The polyimideprecursor is soluble to a developer solution. By irradiating I-line orKrF-line, the PBG in the exposed region generates a base, which is thenquenched by the acid generated from the TAG. In the non-exposed region,the acid generated from the TAG upon heating causes crosslinking. Thedeveloped pattern can be heated to cleave the acid-cleavable group of R3by action of the TAG, if necessary. The acid-cleavable group of R3 canremain in the relief pattern.

Embodiment No. 30 includes a polyimide precursor represented by Formula2 wherein R3 is a base-cleavable group, R4 is a hydrophilic group, andR5 is an acid-cleavable group. It also includes a PBG, and it caninclude a photosensitizer, if necessary. The polyimide precursor issoluble in a developer solution. By irradiating I-line or KrF-line, theexposed region is rendered insoluble in a developer solution. Thedeveloped pattern can be heated to cleave the base-cleavable group ofR3, if necessary. The base-cleavable group of R3 can remain in therelief pattern.

Embodiment No. 31 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a base-cleavable group, and R5 is anacid-cleavable group. It also includes a PBG and TAG, and it can includea crosslinker and a photosensitizer, if necessary. The polyimideprecursor is insoluble in a developer solution, but by irradiatingI-line or KrF-line, the exposed region can be solubilized by the actionof the PBG. After developing a pattern, it is heated so as to cleave theacid-cleavable group of R3 by the action of the TAG.

Embodiment No. 32 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is a thermally-cleavable group,and R5 is hydrogen. It also includes a DNQ, and it can include acrosslinker and a photosensitizer, if necessary. The composition can bepatterned by irradiating I-line or KrF-line. The developed pattern canbe heated to cleave the thermally-cleavable group of R3, if necessary.The thermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 33 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is an acid-cleavable group, andR5 is hydrogen. It also includes a DNQ and PAG, and it can include acrosslinker and a photosensitizer, if necessary. The DNQ decreases thealkali solubility of the polyimide precursor, and can be patterned byI-line irradiation. The developed pattern can be heated to cleave theacid-cleavable group of R3, if necessary. After developing a pattern, itcan be irradiated a second time to cause the PAG to generate an acid soas to cleave R3.

Embodiment No. 34 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is a base-cleavable group, andR5 is hydrogen. It also includes a DNQ and PBG, and it can include acrosslinker and a photosensitizer, if necessary. The DNQ decreases thealkali solubility of the polyimide precursor, and can be patterned byI-line irradiation. The developed pattern can be heated to cleave thebase-cleavable group of R3, if necessary. After developing a pattern, itcan be irradiated a second time to cause the PBG to generate a base soas to cleave R3.

Embodiment No. 35 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by anacid cleavable group, R3 is a thermally-cleavable group, and R5 ishydrogen. It also includes a PAG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide precursor should beinsoluble to a developer solution. The precursor can be designed to beinsoluble to the alkali developer solution, or alternatively, theconcentration of the base component of the developer solution can besignificantly low, e.g., 0.1N or less. The composition can be patternedby irradiating I-line or KrF-line. The developed pattern can be heatedto cleave the thermally-cleavable group of R3, if necessary. Thethermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 36 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by anbase cleavable group, R3 is a thermally-cleavable group, and R5 ishydrogen. It also includes a PBG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide precursor should beinsoluble to a developer solution. The precursor can be designed to beinsoluble to the alkali developer solution, or alternatively, theconcentration of the base component of the developer solution can besignificantly low, e.g., 0.1N or less. The composition can be patternedby irradiating I-line or KrF-line. The developed pattern can be heatedto cleave the thermally-cleavable group of R3, if necessary. Thethermally-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 37 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group, R3 is an acid-cleavable group, andR5 is hydrogen. It also includes DNQ and TAG and it can include acrosslinker and a photosensitizer, if necessary. The DNQ decreases thealkali solubility of the polyimide precursor, and can be patterned byI-line or KrF-line irradiation. The developed pattern can be heated tocleave the acid-cleavable group of R3 by action of the TAG.

Embodiment No. 38 includes a polyimide precursor represented by Formula2 wherein R4 is a hydrophilic group partially or wholly protected by anacid-cleavable group, R3 is a thermally-cleavable group, and R5 ishydrogen. It also includes a PBG and TAG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursorshould be insoluble to a developer solution. The precursor can bedesigned to be insoluble to the alkali developer solution, oralternatively, the concentration of the base component of the developersolution can be significantly low, e.g., 0.1N or less. By irradiatingI-line or KrF-line, the PBG in the exposed region generates a base,which is then quenched by an acid generated from the TAG upon heating.In the non-exposed region, the acid generated from the TAG upon heatingcleaves the acid-cleavable group of R4. After developing a pattern, thethermally cleavable group of R3 can be cleaved, if necessary.

Embodiment No. 39 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes a PBG and TAG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursoris soluble to a developer solution. By irradiating I-line or KrF-line,the PBG in the exposed region generates a base, which is then quenchedby the acid generated from the TAG upon heating. In the non-exposedregion, the acid generated from the TAG upon heating causescrosslinking. The developed pattern can be heated to cleave thethermally-cleavable group of R3, if necessary. The thermally-cleavablegroup of R3 can remain in the relief pattern.

Embodiment No. 40 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes an FRG, and it can include a photosensitizer,if necessary. The polyimide precursor is soluble in a developersolution. By irradiating I-line or KrF-line, the exposed region canbecome insoluble by causing the crosslinking of the polymer. Thedeveloped pattern can be heated to cleave the thermally-cleavable groupof R3, if necessary. The thermally-cleavable group of R3 can remain inthe relief pattern.

Embodiment No. 41 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes a FRG and a TAG, and it can include aphotosensitizer, if necessary. The polyimide precursor is soluble in adeveloper solution. By irradiating I-line or KrF-line, the exposedregion can become insoluble by causing the crosslinking of the polymer.The developed pattern can be heated to cleave the acid-cleavable groupof R3 by the action of the TAG, if necessary. The acid-cleavable groupof R3 can remain in the relief pattern.

Embodiment No. 42 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes a PAG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide precursor is soluble to adeveloper solution, but when I line or KrF line irradiated, the exposedregion can become insoluble by causing the crosslinking of the polymer.After developing a pattern, it can be heated to cleave thethermally-cleavable group of R3, if necessary. The thermally-cleavablegroup of R3 can also remain in the relief pattern.

Embodiment No. 43 includes a polyimide precursor represented by Formula2 wherein R3 is a thermally-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes a PBG, and it can include a crosslinker and aphotosensitizer, if necessary. The polyimide precursor is soluble to adeveloper solution, but by irradiating I-line or KrF-line, the exposedregion can become insoluble by causing the crosslinking of the polymer.After developing a pattern, it can be heated to cleave thethermally-cleavable group of R3, if necessary. The thermally-cleavablegroup of R3 can also remain in the relief pattern.

Embodiment No. 44 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a crosslinkable group, and R5 ishydrogen. It also includes a PBG and TAG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursoris soluble to a developer solution. By irradiating I-line or KrF-line,the PBG in the exposed region generates a base, which is then quenchedby the acid generated from the TAG upon heating. In the non-exposedregion, the acid generated from the TAG upon heating causescrosslinking. The developed pattern can be heated to cleave theacid-cleavable group of R3 by action of the TAG, if necessary. Theacid-cleavable group of R3 can remain in the relief pattern.

Embodiment No. 45 includes a polyimide precursor represented by Formula2 wherein R3 is an acid-cleavable group, R4 is a hydrophilic grouppartially or wholly protected by a base-cleavable group, and R5 ishydrogen. It also includes a PBG and TAG, and it can include acrosslinker and a photosensitizer, if necessary. The polyimide precursorshould be insoluble to a developer solution. The precursor can bedesigned to be insoluble to the alkali developer solution, oralternatively, the concentration of the base component of the developersolution can be significantly low, e.g., 0.1N or less. By irradiatingI-line or KrF-line, the exposed region can become soluble by the actionof the PBG. After developing a pattern, it is heated so as to cleave theacid-cleavable group of R3 by the action of the TAG.

TABLE 2 Photosensitive composition Polyimide precursor represented byFormula 2 R4 Hydrophilic Hydrophilic Hydrophilic group group group R3 R5protected protected protected acid- base- thermally- acid- Hydro- byacid- by base- by cross- Expo- cleavable cleavable cleavable hydro-cleavable philic cleavable cleavable linkable Active sure positive/ No.group group group gen group group group group group Compound⁽¹⁾ Light⁽²⁾negative⁽³⁾ 17 x x x DNQ I or KrF p 18 x x x DNQ + PAG I + KrF p 19 x xx DNQ + PBG I + KrF p 20 x x x PAG I or KrF p 21 x x x PBG I or KrF p 22x x x DNQ + TAG I or KrF p 23 x x x PBG + TAG I or KrF n 24 x x x PBG +TAG I or KrF p 25 x x x FRG I or KrF n 26 x x x FRG + TAG I or KrF n 27x x x PAG I or KrF n 28 x x x PBG I or KrF n 29 x x x PBG + TAG I or KrFp 30 x x x PBG I or KrF n 31 x x x PBG + TAG I or KrF p 32 x x x DNQ Ior KrF p 33 x x x DNQ + PAG I + KrF p 34 x x x DNQ + PBG I + KrF p 35 xx x PAG I or KrF p 36 x x x PBG I or KrF p 37 x x x DNQ + TAG I or KrF p38 x x x PBG + TAG I or KrF n 39 x x x PBG + TAG I or KrF p 40 x x x FRGI or KrF n 41 x x x FRG + TAG I or KrF n 42 x x x PAG I or KrF n 43 x xx PBG I or KrF n 44 x x x PBG + TAG I or KrF p 45 x x x PBG + TAG I orKrF p ⁽¹⁾DNQ represents a diazonaphthoquinone compound, PAG represents aphoto-acid generator, PBG represents a photo-base generator, TAGrepresents a thermal acid generator, and FRG represents a free radicalgenerator. ⁽²⁾I represents an actinic light having wavelength of 365 nm,and KrF represents an actinic light having wavelength of 248 nm.⁽³⁾Lower-case letter p represents a positive-acting composition, andlower-case letter n represents a negative-acting composition.

EXAMPLES

The present invention is hereinafter described based on the Examples ofthe present invention.

Production Examples 1

The compound having a Formula 18 was provided.

In a three-neck flask having a volume of 300 mL, 20.00 grams of thecompound as represented by Formula 18, 10.82 g of3,5-dinitrobenzoylchloride, 4.6 mL of pyridine and 150 mL ofdichloromethane were provided and mixed together in a nitrogenatmosphere at a temperature of 40° C. for a period of three hours. Thereaction liquid was put into an HCl solution having a concentration of0.6 N, thereby forming a white precipitate, which was collected byfiltration. The filtered precipitate was subjected to vacuum drying atroom temperature. The yield was 72% (20.97 g). The results of the NMRspectrum showed that the obtained compound has a structure representedby Formula 19.

Production Example 2

In a three-neck flask having a volume of 300 mL, 9.90 g of the compoundas prepared in Production Example 1, 0.97 g of 10% palladium carbon and75 mL of N,N-dimethylformamide (DMF) were mixed for a period of 12hours. The reaction liquid was subjected to a Celite treatment, and thefiltrate was put into water, thereby forming a precipitate, which wascollected. The collected precipitate was purified by recrystallizationfrom a mixture of water and methanol to obtain a white powder. The yieldwas 57% (5.13 g). The results of the NMR spectrum showed that obtainedcompound has a structure represented by Formula 20.

Production Example 3

In a three-neck flask having a volume of 300 mL, 1.50 g of the compoundas prepared in Production Example 2, 1.19 g of 6FDA(2,2-bis(3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride) and10.8 mL of N,N-dimethylacetamide (DMAc) were mixed for a period of 5hours. The reaction liquid was put into a mixture of methanol and water,precipitating the polymer. The polymer as precipitated was collected byfiltration, and then subjected to vacuum drying at a temperature of 50°C. The yield was 95% (2.5 g). Then, the polymer was dissolved in DMAc toa concentration of 0.1 g/dL. The intrinsic viscosity measured by anOstwald viscometer was 0.4 dL/g. The results of NMR spectrum showed thatthe obtained polymer has a structure represented by Formula 21.

Production Example 4

In a three-neck flask having a volume of 300 mL, 1.50 g of the compoundas prepared in Production Example 2, 0.58 g of PMDA (pyromelliticdianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride) and 8.2 mL ofN,N-dimethylacetamide (DMAc) were mixed for a period of 5 hours. Thereaction liquid was put into a mixture of methanol and water toprecipitate the polymer. The polymer as precipitated was collected byfiltration, and then subjected to vacuum drying at a temperature of 50°C. The yield was 90% (1.87 g). Then, the polymer was dissolved in DMActo become a concentration of 0.1 g/dL. The intrinsic viscosity measuredby an Ostwald viscometer was 0.12 dL/g. The results of the NMR spectrumshowed that the obtained polymer has a structure represented by Formula22.

Production Example 5

In a three-neck flask having a volume of 300 mL, 1.00 g of the compoundas prepared in Production Example 2, 0.20 g of PMDA, 0.40 g of 6FDA and4 mL of N,N-dimethylacetamide (DMAc) were mixed for a period of 5 hours.The reaction liquid was put into a mixture of methanol and water toprecipitate the polymer. The polymer as precipitated was collected byfiltration, and then subjected to vacuum drying at a temperature of 50°C. The yield was 93% (1.49 g). Then, the polymer was dissolved in DMActo become a concentration of 0.1 g/dL. The intrinsic viscosity measuredby an Ostwald viscometer was 0.14 dL/g. The results of the NMR spectrumshowed that the obtained polymer has a structure represented by Formula23.

Production Example 6

In a three-neck flask having a volume of 300 mL, 0.5 g of the polymerobtained by Production Example 3, 0.10 g of pyridine, 0.13 g of aceticanhydride and 4.5 g of were mixed at a temperature of 110° C. for aperiod of 12 hours in a nitrogen atmosphere. The reaction liquid was putinto a mixture of methanol and water to precipitate the polymer. Thepolymer as precipitated was collected by filtration, and then subjectedto vacuum drying at a temperature of 100° C. The yield was 90% (0.43 g).The results of the NMR and IR spectra showed that the obtained polymerhas a structure represented by Formula 24. The intrinsic viscositymeasured by an Ostwald viscometer at a temperature of 30° C. was 0.4dL/g. The IR spectrum is shown in FIG. 1. The polymer having a structurerepresented by Formula 24 was well soluble in a tetramethylammoniumaqueous solution having a concentration of 2.38 wt %. Additionally, thepolymer having a structure represented by Formula 24 was well soluble inacetone, methanol, tetrahydrofuran, and propylene glycol monomethyletheracetate.

Production Example 7

In a three-neck flask having a volume of 300 mL, 1.2 g of the polymerobtained by Production Example 4, 0.27 g of pyridine, 0.32 g of aceticanhydride and 7.0 g of DMF were mixed at a temperature of 110° C. for aperiod of 12 hours in a nitrogen atmosphere. The reaction liquid was putinto a mixture of methanol and water to precipitate the polymer. Thepolymer as precipitated was collected by filtration, and then subjectedto vacuum drying at a temperature of 100° C. The yield was 87% (1.00 g).The results of NMR and IR spectra showed that the obtained polymer has astructure represented by Formula 25. The intrinsic viscosity measured byan Ostwald viscometer at a temperature of 30° C. was 0.12 dL/g. Thepolymer having a structure represented by Formula 25 was well soluble ina tetramethylammonium aqueous solution having a concentration of 2.38 wt%. Additionally, the polymer having a structure represented by Formula25 was well soluble in methanol, tetrahydrofuran, and propylene glycolmonomethylether acetate.

Production Example 8

In a three-neck flask having a volume of 300 mL, 1.2 g of the polymerobtained by Production Example 5, 0.27 g of pyridine, 0.32 g of aceticanhydride and 7.0 g of DMF were mixed at a temperature of 110° C. for aperiod of 12 hours in a nitrogen atmosphere. The reaction liquid was putinto a mixture of methanol and water to precipitate the polymer. Thepolymer as precipitated was collected by filtration, and then subjectedto vacuum drying at a temperature of 100° C. The yield was 87% (1.00 g).The results of NMR and IR spectra showed that the obtained polymer has astructure represented by Formula 26. The intrinsic viscosity measured byan Ostwald viscometer at a temperature of 30° C. was 0.12 dL/g. Thepolymer having a structure represented by Formula 26 was well soluble ina tetramethylammonium aqueous solution having a concentration of 2.38 wt%. Additionally, the polymer having a structure represented by Formula26 was well soluble in methanol, tetrahydrofuran, and propylene glycolmonomethylether acetate.

Example 1

Diazonaphthoquinone as represented by the following Formula 27 wasprovided.

In Formula 27, G represents hydrogen and/or the Formula 28 at a ratio ofapproximately 34/66 and is herein referred to as “THBP”.

Into a vessel, 15 parts by weight of the polyimide resin obtained inProduction Example 6, 5 parts by weight of the THBP having Formula 27,and 80 parts by weight of propylene glycol methyl ether acetate (PGMEA)were mixed together. After homogeneously mixed, the mixture wasfiltrated to prepare Sample A. Thus, the THBP was included at an amountof 5 wt % in the resist composition, and at an amount of 25 wt % in thesolid contents of the resist composition.

Example 2

Sample B was prepared in the same manner as Example 1 except for adding16 parts by weight of the polyimide resin obtained in Production Example6, and 4 parts by weight of the THBP having formula. Thus, the THBP wasincluded at an amount of 4 wt % in the resist composition, and at anamount of 20 wt % in the solid contents of the resist composition.

Example 3

Sample C was prepared in the same manner as Example 1 except for adding17 parts by weight of the polyimide resin obtained in Production Example6, and 3 parts by weight of the THBP having formula. Thus, the THBP wasincluded at an amount of 3 wt % in the resist composition, and at anamount of 15 wt % in the solid contents of the resist composition.

Comparative Example 1

Sample D was prepared in the same manner as Example 1 except for adding20 parts by weight of the polyimide resin obtained in Production Example6. Thus, the THBP was not included in the resist composition.

Each of the Samples A to D was applied to a silicon substrate by meansof spin coating at a rotation speed of 1000 rpm for a period of 30seconds. Then, the silicon substrate was heated at a temperature of 80°C. for a period of 3 minutes, obtaining a film, having a thickness of1.5 μm.

The surface of the film was covered by a mask having a pattern with sizeof line/space=150 μm/220 p.m. Thereafter, it was exposed to I-line,having a wavelength of 365 nm at a dose amount of 2 J/cm². After theradiation, the film was developed in a tetramethylammonium hydroxideaqueous solution having a concentration of 0.26 N. Then, the film wascured at a temperature of 250° C. for a period of 30 minutes.

The dissolution rates (DRs) in tetramethyl ammonium hydroxide aqueoussolution were measured using a custom-made spectroscopic reflectometerbased DR monitor. FIG. 2 shows the relationship of the dissolution ratesbetween the exposed region and non-exposed regions. In FIG. 2, “THBPloading” means the THBP concentration is the solid contents of theresist composition. Samples A to C showed sufficient difference betweenthe dissolution rates on the exposed region and the non-exposed region.For example, the exposed region of Sample B, including THBP at aconcentration of 20 wt % in the solid contents, had a dissolution rate45-times more than the non-exposed region. The relationship obtained inthe present invention was found to be sufficient for carrying out resistpatterning.

With respect to the resist composition of Example 2, the dose amount ofthe I-line was varied to examine the sensitivity of the composition.FIG. 3 shows the results. The resulting contrast curve for this materialshows that the material exhibits a sensitivity of approximately 170mJ/cm² and a contrast of 1.32.

FIG. 4 shows SEM pictures taken with respect to the developed patternformed from the photosensitive composition of Example 2 with a doseamount of 210 mJ/cm². The film was cured at a temperature of 250° C. fora period of 30 minutes. The obtained pattern of the polyimide on thesilicon substrate corresponded to the pattern of the mask used. Inparticular, the lines of the polyimide were clearly formed with aninterval of 150 μm.

FIG. 5 shows a mass spectrum of the polyimide as represented by Formula24 at 250° C. In the spectrum, a parent peak at M/z of 425.9 wasconsistent with the mass number of HFA-containing side-group, and thesuccessive elimination of CF₃ groups was also detected.

By means of a thermal gravimetric measurement, the side-group cleavagewas observed under a significantly low temperature (100-200° C.) in thepolyimide as represented by Formula 24 by mixing with eitherp-toluenesulfonic acid or camphor sulfonic acid, and the mixture of thepolyimide as represented by Formula 24 or the acid which was generatedby mixing in a triphenylsulfonium hexafluoroantimonate (photoacidgenerator (PAG)) and 9-anthracene methanol (photosensitizer) with thepolymer and subsequently exposing the mixture to broadband UV light andheating the film. After the side-group cleavage, the film was insolublein the developer solution and was measured to have a dielectric constantof 2.60 at a frequency of 1 MHz (dielectric constant before side groupcleavage was measured as 3.30). This reduction in the dielectricconstant as a result of the side group cleavage is very desirable fordielectric applications, and thus shows one advantage of such a materialcontaining cleavable, solubilizing functional groups.

1. A photosensitive composition, comprising: a polyimide comprising arepeating unit as represented by Formula 1:

where R1 represents an aliphatic, alicyclic, aromatic or heterocyclicgroup; R2 represents an aliphatic, alicyclic, aromatic or heterocyclicgroup; R3 represents at least one of the following formulas:

where A represents R4; R6, R7, R17, and R18 each represents an organicgroup having a carbon number of 1 to 40; r and q each represents aninteger of 0 or 1; and i represents an integer of 1 or more;

where A represents R4; R8 and R28 each represents hydrogen or an organicgroup having a carbon number of 1 to 40; R9, R19, and R20 eachrepresents an organic group having a carbon number of 1 to 40; n, s, andt each represents an integer of 0 or 1; and i represents an integer of 1or more;

where A represents R4; R21 and R22 each represents an organic grouphaving a carbon number of 1 to 40; u and v each represents an integer of0 or 1; and i represents an integer of 1 or more;

where A represents R4; R11 and R12 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R23 and R24 eachrepresents an organic group having a carbon number of 1 to 40; w and xeach represents an integer of 0 or 1; and i represents an integer of 1or more;

where A represents R4; R13, R14 and R15 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R25 and R26 eachrepresents an organic group having a carbon number of 1 to 40; y and zeach represents an integer of 0 or 1; and i represents an integer of 1or more; R4 represents a monofunctional hydrophilic group or amonofunctional hydrophilic group protected by second acid-cleavablegroup, second base-cleavable group, or crosslinkable cleavable group;and, h represents an integer of 1 or more; and a photosensitiveadditive.
 2. A photosensitive composition, comprising: a polyimideprecursor comprising a repeating unit as represented by Formula 2:

where R1 represents an aliphatic, alicyclic, aromatic or heterocyclicgroup; R2 represents an aliphatic, alicyclic or aromatic group; R3represents at least one of the following formulas:

where A represents R4; R6, R7, R17, and R18 each represents an organicgroup having a carbon number of 1 to 40; r and q each represents aninteger of 0 or 1; and i represents an integer of 1 or more;

where A represents R4; R8 and R28 each represents hydrogen or an organicgroup having a carbon number of 1 to 40; R9, R19, and R20 eachrepresents an organic group having a carbon number of 1 to 40; n, s, andt each represents an integer of 0 or 1; and i represents an integer of 1or more;

where A represents R4; R21 and R22 each represents an organic grouphaving a carbon number of 1 to 40; u and v each represents an integer of0 or 1; and i represents an integer of 1 or more;

where A represents R4; R11 and R12 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R23 and R24 eachrepresents an organic group having a carbon number of 1 to 40; w and xeach represents an integer of 0 or 1; and i represents an integer of 1or more;

where A represents R4; R13, R14 and R15 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R25 and R26 eachrepresents an organic group having a carbon number of 1 to 40; y and zeach represents an integer of 0 or 1; and i represents an integer of 1or more; R4 represents a monofunctional hydrophilic group or amonofunctional hydrophilic group protected by second acid-cleavablegroup, second base-cleavable group or crosslinkable cleavable group; R5represents hydrogen or a third acid-cleavable group, and h represents aninteger of 1 or more; and a photosensitive additive.
 3. A photosensitivecomposition according to claim 1 or 2, wherein the photosensitiveadditive comprises a diazonaphthoquinone compound, a photo-acidgenerator, a photo-base generator, a free radical generator, orcombinations thereof, and wherein the photosensitive additivedifferentiates the dissolution rate of the exposed areas versus thenon-exposed areas in a developer solution in order to form a reliefpattern.
 4. A photosensitive composition according to claim 3, furthercomprising a thermal acid generator, a crosslinker, a photosensitizer,or combinations thereof.
 5. A photosensitive composition according toclaim 1 or 2, wherein R3 represents an organic group represented byFormula 3 or Formula 3a:

where A represents R4; R6, R7, R17, and R18 each represents an organicgroup having a carbon number of 1 to 40; r and q each represents aninteger of 0 or 1; and i represents an integer of 1 or more.
 6. Aphotosensitive composition according to claim 1 or 2, wherein R3represents an organic group represented by Formula 4 or Formula 4a:

where A represents R4; R8 and R8 each represents hydrogen or an organicgroup having a carbon number of 1 to 40; R9, R19, and R20 eachrepresents an organic group having a carbon number of 1 to 40; n, s, andt each represents an integer of 0 or 1; and i represents an integer of 1or more.
 7. A photosensitive composition according to claim 1 or 2,wherein R3 represents an organic group represented by Formula 5 orFormula 5a:

where A represents R4; R21 and R22 each represents an organic grouphaving a carbon number of 1 to 40; u and v each represents an integer of0 or 1; and i represents an integer of 1 or more.
 8. A photosensitivecomposition according to claim 1 or 2, wherein R3 represents an organicgroup represented by Formula 6 or Formula 6a:

where A represents R4; R11 and R12 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R23 and R24 eachrepresents an organic group having a carbon number of 1 to 40; w and xeach represents an integer of 0 or 1; and i represents an integer of 1or more.
 9. A photosensitive composition according to claim 1 or 2,wherein R3 represents an organic group represented by Formula 7 orFormula 7a:

where A represents R4; R13, R14 and R15 each represents hydrogen or anorganic group having a carbon number of 1 to 40; R25 and R26 eachrepresents an organic group having a carbon number of 1 to 40; y and zeach represents an integer of 0 or 1; and i represents an integer of 1or more.
 10. A photosensitive composition according to claim 1 or 2,wherein R4 represents an organic group represented by Formula 8:

where R16 represents hydrogen, an acid-cleavable group, a base-cleavablegroup or a crosslinkable group.
 11. A photosensitive compositionaccording to claim 1 or 2, wherein R4 represents an organic grouprepresented by Formula 9:—OR¹⁶  Formula 9 where R16 represents hydrogen, an acid-cleavable group,a base-cleavable group or a crosslinkable group.
 12. A photosensitivecomposition according to claim 1 or 2, wherein R4 represents an organicgroup represented by Formula 10:—COOR¹⁶  Formula 10 where R16 represents hydrogen, an acid-cleavablegroup, a base-cleavable group or a crosslinkable group.
 13. Aphotosensitive composition according to claim 1 or 2, wherein R4represents an organic group represented by Formula 11:—SO₃R¹⁶  Formula 11 where R16 represents hydrogen, an acid-cleavablegroup, a base-cleavable group or a crosslinkable group.
 14. Aphotosensitive composition according to claim 1 or 2, wherein R4represents an organic group represented by Formula 12:—NR¹⁶—SO₂CF₃  Formula 12 where R16 represents hydrogen, anacid-cleavable group, a base-cleavable group or a crosslinkable group.15. A photosensitive composition according to claim 10, wherein R1represents an organic group represented by Formula 13, R3 represents anorganic group represented by Formula 14, wherein A represents R4, and mrepresents an integer of 1, 2, 3, 4 or 5:


16. A photosensitive composition according to claim 10, wherein R1represents an organic group represented by Formula 13, R3 represents anorganic group represented by Formula 15, wherein D represents R4, and orepresents an integer of 1, 2, 3, 4 or 5:


17. A photosensitive composition according to claim 10, wherein R1represents an organic group represented by Formula 13, R3 represents anorganic group represented by Formula 16, wherein E represents R4, and prepresents an integer of 1, 2, 3, 4 or 5: